KR102193237B1 - Non-Fluorinated Water-repellant surface-treating composition having high water-glinding property and manufacturing method thereof - Google Patents

Abstract

According to the present invention, (a) as a water repellent component, an organopolysiloxane sol prepared by adding a reactive silicone polymer solution to a mixture of a silicone precursor, a silicone crosslinking agent and a solvent, (b) an N-polyoxyalkylenated fatty acid as a cloudability improving agent. A non-fluorine-based water-repellent surface treatment composition comprising at least one compound selected from the group consisting of amide or O-alkylated polyglucoside, (c) an acidic catalyst selected from organic or inorganic acids, and (d) an aqueous solvent, a preparation method thereof, A water-repellent permeable and impermeable article is provided using this.
The non-fluorine-based water-repellent surface treatment composition according to the present invention is stable and economical to manufacture, and can maintain colorless and transparent properties even during long-term storage, so it has high stability and storage properties, as well as high adhesion to permeable articles such as fabrics, Excellent water repellency and rolling properties can be imparted.

Description

Non-Fluorinated Water-repellant surface-treating composition having high water-glinding property and manufacturing method thereof {Non-Fluorinated Water-repellant surface-treating composition having high water-glinding property and manufacturing method thereof}

The present invention relates to a non-fluorine-based water-repellent surface treatment composition with improved cloudability, and a method for producing the same, and specifically, an organopolysiloxane sol as a water-repellent component and an N-polyoxyalkylenated fatty acid amide or O-alkylated polyglucoside as a cloudability improving agent. It relates to a non-fluorine-based water-repellent surface treatment composition having excellent rolling properties and a manufacturing method thereof. The non-fluorine-based water repellent composition according to the present invention can impart excellent water repellency and rolling properties to permeable articles such as fabrics.

Items including windshields, shower booths, veranda windows, car windshields, car side mirrors, ship exteriors, electronics, mobile phones, etc., may be exposed to water, and contaminants dissolved or mixed in water The product is contaminated and its lifespan is shortened. In particular, in the case of items used in automobiles and ships, there is a problem in safety of operation.

Therefore, it is possible to prevent contamination of the article by using a material exhibiting water repellency. In this case, since the material exhibiting water repellency is relatively expensive, a method of coating the surface of the article with a thin thickness to prevent contamination is adopted.

In general, for articles (hereinafter referred to as permeable articles) that exhibit air, water, and water permeability, such as fibers, knitted fabrics, woven fabrics, and nonwovens, materials with low surface energy such as fluorinated polymers and silane polymers are used as water repellent agents. Or, it imparts water repellency as a hydrophobic agent. Until now, a fluorine-based water-repellent material, which has a chemical structure based on a fluorine molecule, is made by combining a fluorine-based material with an inorganic material or using an organic material containing fluorine has been mainly used. For example, organopolysilane containing a perfluoroalkyl group, which is one of the fluorinated polymers, has a very small surface free energy and has high water repellency, and is excellent in chemical resistance due to the perfluoroalkyl group. In addition, it has good adhesion to substrates such as glass, plastic, and cloth. Recently, a non-fluorine-based water-repellent material having a structure similar to this and based on silicon or long hydrogen bonds has been developed, and now shows relatively low performance compared to fluorine-based materials.

However, fluorine-based water-repellent materials including perfluoroalkyl group-containing organopolysilanes and non-fluorine-based water-repellent materials including silane polymers have excellent water repellency, but there is a problem that the rolling property, which is the property of rolling or sliding of water droplets, is poor. It was difficult to use for required articles, and in a permeable article such as a fabric, there is an inconvenience that water exceeding the water repellency will seep into the fabric and cause surface wetting if it contacts the surface or stays for a long time. In addition, long-term stability is also required to have marketability, but long-term stability is often insufficient.

On the other hand, permeable articles such as fabrics are often required to have moisture-permeable and waterproof properties, and water-repellent treatment can be applied for this. In order to impart water repellency to permeable articles such as fabrics without impairing the permeability, not only water repellency, which is a property of not forming or adhering to water droplets on the surface, but also water droplets on the surface of the fabric flow or roll without staying or stagnating. It is also necessary to consider the surface cloudiness of falling.

Patent Document 1 (Korean Publication No. 10-2015-0081177, publication date July 13, 2015) includes 2 million to 4 million needle-shaped nano structures per 1 mm ^{2 of} area. Nanoacicular-fibers having a surface of 5 to 100 nm in thickness; In addition, a superhydrophobic fiber having a contact angle of 150 degrees or more and a rolling angle of 3 degrees or less and a manufacturing method is disclosed, which is located on a surface including the nanostructures and includes a coating layer containing a hydrophobic material.

In Patent Document 2 (Korean Publication No. 10-2016-0060913, publication date May 31, 2016), a sol-gel dispersion in which nanoparticles were aggregated was prepared using a solvent having a dielectric constant of 20 or less, and the surface And then impregnated with hydrophobic silane to hydrophobize the surface, thereby providing a method for producing a super-water-repellent surface in which the surface rolling angle converges to 0 degrees.

In Patent Document 3 (Korean Registration No. 10-1831380, registration date February 14, 2018), a sol-gel reaction by mixing an organopolysilane containing a perfluoroalkyl group, an alkylamide or alkyl polyglucoside, an acid and a solvent It is disclosed that the water-repellent surface treatment agent excellent in adhesion to the substrate, water repellency, and surface lubricity can be produced by causing this. However, the water-repellent surface treatment agent disclosed in the document is for forming a water-repellent surface having lubricity on the impermeable substrate, and there is no description of water repellency and/or rollability in a permeable article such as a fabric.

In general, in a permeable article through which water and air can permeate, specifically, in a permeable article through which liquids such as water and oil and gases such as air and water vapor can permeate, water repellency is maintained while maintaining the moisture permeability characteristic of the permeable article. It is not easy to give. For example, in order to use the fabric as a water-permeable water-repellent fabric by water-repellent treatment, the surface of the water-repellent-treated fabric is required to have excellent rolling properties (low rolling angle) in addition to excellent water repellency (or high contact angle). Wearable fabrics using conductive carbon fiber, sportswear with internal wiring, and fire-resistant fabrics for firefighters have high water repellency even when in contact with water for a long time, but have high rolling properties that can avoid long-term contact with water as much as possible. Is being demanded. Therefore, development of a water-repellent surface treatment agent excellent in not only water repellency but also rolling property is desired.

Under these circumstances, the present invention was developed to meet the need for a new non-fluorine-based water-repellent surface treatment composition for imparting high water repellency and excellent surface rollingability to permeable articles such as fabrics.

Domestic Publication No. 10-2015-0081177 (Publication date 2015.07.13.) Domestic Publication No. 10-2016-0060913 (Publication date 2016.05.31) Domestic Registration Gazette No. 10-1831380 (Registration Date 2018.02.14)

The present invention comprises a water-repellent component comprising an organopolysiloxane sol and an optional reactive silicone polymer solution, and a rolling property improving agent comprising an N-polyoxyalkylenated fatty acid amide or O-alkylated polyglucoside, having excellent rolling properties It is intended to provide a treatment composition and a method for preparing the same.

The present invention is also intended to provide a water-repellent article, particularly a permeable article such as a fabric, using the water-repellent surface treatment composition.

The inventors,

(a) as a water-repellent component, an organopolysiloxane sol prepared by adding a reactive silicone polymer solution to a mixture of a silicone precursor, a silicone crosslinking agent, and a solvent,

(b) at least one compound selected from the group consisting of N-polyoxyalkylenated fatty acid amide or O-alkylated polyglucoside as a rolling property improving agent,

(c) an acidic catalyst selected from organic or inorganic acids, and

(d) aqueous solvent

It was found that the non-fluorine-based water-repellent surface treatment composition comprising, not only has excellent stability and long-term storage, but also can impart excellent water repellency and high rolling properties to permeable articles such as fabrics, and completed the present invention.

The non-fluorine-based water-repellent surface treatment composition may be prepared by a method comprising the following steps:

(Step 1) preparing a mixture comprising a silicon precursor, a silicon-based crosslinking agent, and an aqueous solvent;

(Step 2) preparing an organopolysiloxane primary sol solution by adding an acidic catalyst to the mixture to perform a sol-gel reaction; And

(Step 3) Into the organopolysiloxane primary sol solution, at least one compound selected from the group consisting of N-polyoxyalkylenated fatty acid amide or O-alkyl polyglucoside and a reactive silicone polymer solution are simultaneously added, Preparing an organopolysiloxane secondary sol solution, which is a reaction product of an unreacted silicone crosslinking agent in a sol solution and a reactive silicone polymer.

The non-fluorine-based water-repellent surface treatment composition according to the present invention is stable and economical to manufacture, and can maintain colorless and transparent properties even during long-term storage, so it has high stability and storage properties, as well as high adhesion to permeable articles such as fabrics, Excellent water repellency and rolling properties can be imparted.

The first object of the present invention is to provide a non-fluorine-based water-repellent surface treatment composition comprising the following components:

(a) as a water-repellent component, an organopolysiloxane sol prepared by adding a reactive silicone polymer solution to a mixture of a silicone precursor, a silicone crosslinking agent, and a solvent,

(b) at least one compound selected from the group consisting of N-polyoxyalkylenated fatty acid amide or O-alkylated polyglucoside as a rolling property improving agent,

(c) an acidic catalyst selected from organic or inorganic acids, and

(d) an aqueous solvent.

A second object of the present invention is to provide a water-repellent surface treatment composition having excellent rolling properties, and may include the following steps.

(Step 1) preparing a mixture comprising a silicon precursor, a silicon-based crosslinking agent, and an aqueous solvent;

(Step 2) preparing an organopolysiloxane primary sol solution by adding an acidic catalyst to the mixture to perform a sol-gel reaction; And

(Step 3) Into the organopolysiloxane primary sol solution, at least one compound selected from the group consisting of N-polyoxyalkylenated fatty acid amide or O-alkyl polyglucoside and a reactive silicone polymer solution are simultaneously added, Preparing an organopolysiloxane secondary sol solution, which is a reaction product of an unreacted silicone crosslinking agent in a sol solution and a reactive silicone polymer.

A third object of the present invention is to provide a permeable article manufactured using the non-fluorine-based water-repellent surface treatment composition having excellent rolling properties and excellent in water repellency and rolling properties, wherein the permeable article is a fiber, a knitted fabric, a woven fabric, or a nonwoven fabric. Can be chosen.

The present invention will be described in more detail below.

(1) Organopolysiloxane sol solution

The organopolysiloxane sol used as a water-repellent component in the present invention or a solution containing the same may be prepared by a method comprising the following steps (1), (2) and (3):

(Step 1) preparing a mixture comprising a silicon precursor, a silicon-based crosslinking agent, and an aqueous solvent;

(Step 2) preparing an organopolysiloxane primary sol solution by adding an acidic catalyst to the mixture to perform a sol-gel reaction; And

(Step 3) Into the organopolysiloxane primary sol solution, at least one compound selected from the group consisting of N-polyoxyalkylenated fatty acid amide or O-alkyl polyglucoside and a reactive silicone polymer solution are simultaneously added, Preparing an organopolysiloxane secondary sol solution, which is a reaction product of an unreacted silicone crosslinking agent in a sol solution and a reactive silicone polymer.

In the manufacturing method of the present invention, step 1) may be performed at a temperature of 10 to 40° C., preferably at room temperature, using a reactor, kneader or mixer equipped with a stirring device and a thermometer. The order and method of addition of the constituents in step 1), and the mixing method and conditions are not particularly limited and may be performed according to what is commonly used in the art. For example, the constituents may be administered sequentially or simultaneously in a reactor at a temperature of, for example, 10 to 40° C., preferably room temperature, and stirred or kneaded.

The mixture of step 1) contains 20 to 100 parts by weight of a silicon precursor, preferably 35 to 50 parts by weight, more preferably 40 to 50 parts by weight, and 200 to 500 parts by weight of an aqueous solvent based on 100 parts by weight of the silicone crosslinking agent. It may be included in an amount by weight, preferably 250 to 400 parts by weight, more preferably 300 to 400 parts by weight. If the silicon precursor is contained in an amount of less than 20 parts by weight based on 100 parts by weight of the silicone-based crosslinking agent, the molecular weight of the organopolysiloxane precursor solution decreases, making it difficult to form a water-repellent coating layer with a stable three-dimensional network structure on the fiber surface, or the density of the water-repellent coating layer is remarkably low. It may be difficult to express the desired physical properties, such as deterioration and peeling easily by impact, the amount of unreacted crosslinking agent increases, and the degree of improvement of the desired physical properties may be insignificant. If the silicon precursor is included in an amount exceeding 100 parts by weight, the formation of the organopolysiloxane sol solution described later may not be smooth, and thus the desired physical properties may be insignificant when coated on the fiber surface.

The silicon precursor is [3-(trimethoxysilyl)propyl]-octadecyldimethylammonium chloride, 3(3-triethoxysilylpropyl)-5,5-dimethylhydantoin, potassium trimethylsilanolate, triiso Propylsilanol, methoxydimethyloctylsilane, (3-chloropropyl)triethoxysilane, (3-chloropropyl)dimethoxymethylsilane, octadecyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (Trimethoxysilyl) propylmethacrylate, N-[3-(trimethoxysilyl)propyl]-ethylenediamine and 3-glycidoxypropyltrimethoxysilane may contain at least one selected from the group consisting of have.

The silicone-based crosslinking agent is methoxysilane, ethoxysilane, propoxysilane, isopropoxysilane, aryloxysilane, tetramethylorthosilicate (TMOS), tetraacetylorthosilicate (TEOS), and tetrapropylorthosilicate (TPOS). ) It may include one or more selected from the group consisting of.

According to one variant of the present invention, the silicone crosslinking agent may further contain a perfluoroalkyl group-containing organopolysilane represented by the following Formula 1:

[Formula 1]

CF ₃ -(CF ₂ ) _n -R-SiX _p Y _3-p

In the above formula, n is an integer from 0 to 12,

R is an organic group having 1 to 10 carbon atoms or a group containing a silicon atom and an oxygen atom,

X is H or a monovalent hydrocarbon group having 1 to 4 carbon atoms, or a substituent selected from a derivative of the group,

p is 0, 1 or 2,

Y is a C1-C4 alkoxy group, an acyloxy group, or a halogen atom.

The aqueous solvent may be used without limitation in the case of a solvent capable of hydrolyzing a silicon precursor, and as a non-limiting example thereof, at least one selected from the group consisting of a low-cost alcohol having 1 to 4 carbon atoms, water, glycerol and glycol It may include, and preferably water or a mixed solvent of water and a low-cost alcohol may be used.

In the present invention, the step is carried out by a sol-gel reaction using an acidic catalyst. The sol-gel reaction may be carried out at a temperature of 50 to 70°C, preferably 55 to 60°C for 30 to 80 minutes, preferably 40 to 60 minutes. If the temperature is less than 50°C, the reaction time may be delayed or the sol may not be formed smoothly. If the temperature exceeds 70°C, there may be problems such as decomposition reaction in the sol-type reaction product. In addition, the reaction of step 2) is preferably carried out until the solution becomes transparent.

In the above step 2), smooth formation of sol can be promoted by adjusting the pH of the mixture to an appropriate range, for example, pH 3 to 6, preferably pH 4.5 to 5.0, using an acid or an acidic solution. Acids that can be used include, without limitation, hydrochloric acid, nitric acid, sulfuric acid or acetic acid. The concentration and amount of the acid or acid solution are not particularly limited in the present invention as long as the pH of the mixture satisfies the above range. Preferably, acetic acid can be added in an amount of 0.5 to 10 parts by weight, more preferably 1.5 to 3 parts by weight, based on 100 parts by weight of the silicone-based crosslinking agent. In order to produce a more smooth sol, it may be added dropwise or added gradually or gradually while checking the pH of the reaction mixture from time to time.

Next, in the step 3), in the organopolysiloxane primary sol solution, at least one compound selected from the group consisting of a reactive silicone polymer solution and an N-polyoxyalkylenated fatty acid amide or an O-alkylated polyglucoside is simultaneously added. While adding or adding, it may be performed for 40 to 120 minutes at a temperature of 30 to 40°C. In step 3), a reaction product of an unreacted silicone crosslinking agent and a reactive silicone polymer in the primary sol solution may react to form an organopolysiloxane sol.

In the present invention, the reactive silicone polymer may be a silicone oil containing a reactive functional group at least one of a carboxyl group, a hydroxy group and an azo group or an amino group at the end of the polymer main chain or the end of the side chain, preferably containing an amino group as a reactive functional group. It can be chosen from silicone oils. The reactive silicone polymer is 3 having improved durability and high water repellency through reaction with the organopolysiloxane primary sol, for example, through thermal curing with a silicon precursor such as 3-glycidoxypropyltrimethoxysilane. It is possible to form a cross-linked product of organopolysilonic acid having a dimensional network structure. As a silicone oil that can be used as the reactive silicone polymer, mention may be made of polydimethylsilane (PDMS), preferably a polydimethylsilane containing an amino group or an azo group as a reactive functional group.

The reactive silicone polymer may be used in an amount of 10 to 50 parts by weight, more preferably 15 to 25 parts by weight, based on 100 parts by weight of the silicone-based crosslinking agent in step 1). If the reactive silicone polymer is contained in less than 10 parts by weight, it is difficult to form a crosslinked product of organopolysilonic acid having a three-dimensional network structure with high durability and high water repellency, and if the reactive silicone polymer is contained in more than 50 parts by weight There may be a problem of insignificant improvement in physical properties and an increase in cost due to the large number of unreacted reactive silicone polymers.

The reactive silicone polymer that can be used in the present invention preferably has a viscosity of 700 to 1500 cps. If the viscosity is less than 700 cps, the organopolysiloxane secondary sol having the desired molecular weight cannot be formed, so the durability of the cross-linked organopolysilonic acid having a three-dimensional network structure decreases, and the water repellency may decrease due to the decrease in density. have. If the viscosity exceeds 1500 cps, the touch of the water-repellent coated surface is markedly deteriorated, and in the case of water-repellent coating of permeable articles such as fibers or fabrics, the touch and drape properties of the fabricated fabric decrease as their flexibility decreases. There is a problem that can get very bad.

The reactive silicone polymer, for example, through thermal curing with a silicon precursor such as 3-glycidoxypropyltrimethoxysilane, a crosslinked product of organopolysilonic acid having a three-dimensional network structure having improved durability and high water repellency Can be formed.

It is preferable to use the reactive silicone polymer in the form of a solution containing a solvent to dissolve it. The solvent may be used without limitation in the case of a known solvent suitable for dissolving a known reactive silicone polymer, and a non-limiting example thereof may include isopropyl alcohol, and 100 parts by weight of the reactive silicone polymer It can be used in ~150 parts by weight.

Step 3) is carried out by reacting at a temperature of 25 to 45°C, preferably 30 to 40°C for 30 to 120 minutes, preferably 40 to 80 minutes to induce a reaction between the unreacted silicone crosslinking agent and the reactive silicone polymer. The ganopolysiloxane secondary sol may be formed, but the reaction temperature and time are not limited thereto. Therefore, after the step is finished, before the reactive silicone polymer solution is added, the organopolysiloxane primary sol solution is cooled to a temperature range of 25 to 45°C, preferably 30 to 40°C, and then the reactive silicone polymer solution And at least one compound selected from the group consisting of N-polyoxyalkylenated fatty acid amide or O-alkyl polyglucoside is preferably added at the same time. For a temperature increase and/or a homogeneous reaction according to the reaction, a reactive silicone polymer solution and at least one compound selected from the group consisting of an N-polyoxyalkylenated fatty acid amide or an O-alkyl polyglucoside is preferably slowly added. If the reaction temperature is less than 25°C, the reaction time may be delayed or the formation of the organopolysiloxane secondary sol solution may not be smooth.If the temperature exceeds 45°C, a decomposition reaction of the reactive silicone polymer or gelation may occur rapidly. There may be problems such as progress.

According to one preferred embodiment of the present invention, the silicone precursor is 3-glycidoxypropyltrimethoxysilane, and the reactive silicone polymer may be a silicone oil containing an amino group as a reactive functional group. According to this, the water-repellent surface treatment composition for fabrics prepared through the above-described manufacturing method comprises both an organopolysiloxane primary sol and an organopolysiloxane secondary sol in one solution, preferably the organopolysiloxane primary sol Silver contains a glycidoxypropyl group, and the organopolysiloxane secondary sol may contain an amino group at one end, both ends or side chain ends of the main chain.

(2) rolling property improvement agent

According to one embodiment of the present invention, the cloudability improving agent is a hydrophobic group having a long-chain alkyl group having 8 to 36 carbon atoms, preferably 12 to 32, and a polyoxyalkylene group or a polyglucoside group having excellent chemical stability as a hydrophilic group. Compounds, for example N-polyoxyalkylenated fatty acid amides or O-alkyl polyglucosides.

In the present invention, the N-polyoxyalkylenated fatty acid amide is an amide derivative of a long-chain fatty acid in the range of 8 to 36 carbon atoms, and in the nitrogen atom of the amide group, 3 to 20 oxyalkylene groups, preferably 4 to It may be a compound substituted with 14 oxyalkylene groups, more preferably 5 to 10 oxyalkylene groups.

The long-chain fatty acids are tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, hencosanoic acid, decosanoic acid, tetracosanoic acid , Pentacosanoic acid, tricosanoic acid, hexacosanoic acid, triacontanoic acid, dotriacontanoic acid, tetratriacontanoic acid, gentriacontanoic acid, pentatriacontanoic acid, hexatriacontanoic acid, Myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid and hexatriisocontanoic (C36) acid, oleic acid, palmitoleic acid, linolenic acid and cetoleic acid, and analogs thereof may be selected from the group consisting of.

The alkylene group of the polyoxyalkylene group may be selected from the group consisting of ethylene, propylene, isopropylene, butylene, isobutylene, and mixtures thereof, preferably ethylene or propylene.

A typical example of an N-polyoxyalkylenated fatty acid amide may be a compound represented by Formula 2:

[Formula 2]

RC0NH(A0) _n H or RCON[(A0) _n H] ₂

In the above formula,

R represents a substituted or unsubstituted alkyl group having 8 to 36 carbon atoms,

(A0) _n represents polyoxyethylene, polyoxypropylene or polyoxyethylene/polyoxypropylene block copolymer,

n represents an integer of 3 to 20, preferably 4 to 14, more preferably 5 to 10.

Non-limiting examples of the N-polyoxyalkylenated fatty acid amide represented by Formula 2 include polyoxyethylene lauramide, polyoxyethylene stearamide, polyoxyethylene cocamide, polyoxypropylene cocamide, and polypropylene glycol 2-hydro Mention may be made of oxyethyl isostearamide and polypropylene glycol 2-hydroxyethyl cocamide. They can be prepared by polyalkoxylation of fatty acid monoalkanolamides (eg, addition of ethylene oxide or propylene oxide), or by fatty acid amidation with polyalkylene glycols.

In the present invention, the O-alkyl polyglucoside is a compound in which an alkyl group is bonded to at least one of the hydroxy groups (OH) of the polyclucoside by ether linkage, for example, O-alkyl polyglucoside represented by the following formula (3). It can be represented by glucoside:

[Formula 3]

In the above formula,

y is 0 to 6, preferably 1 to 4,

R is an alkyl group having 8 to 36 carbon atoms, preferably 12 to 32 carbon atoms.

The content of the rolling property improving agent may be included in an amount of 0.001 to 20 parts by weight, preferably 0.01 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight based on 100 parts by weight of the silicone-based crosslinking agent of step (A). . When the rolling property improving agent is used in an amount included in the above range, the water-repellent surface treatment composition can provide a transparent coating while exhibiting desired rolling properties, and a flat coating surface can be obtained.

When both N-polyoxyalkylenated fatty acid amide and O-alkyl polyglucoside are used as the cloudability improving agent, the mixing ratio thereof is 100:0.1 to 0.1:100, preferably 100:1 to 1:100 by weight. , More preferably, it may be selected from the range of 100:10 to 10:100. When used in a proportion included in the above range, the water-repellent surface treatment composition can provide a water-repellent surface having high rolling properties as well as excellent washing durability.

In the present invention, the N-polyoxyalkylenated fatty acid amide and O-alkyl polyglucoside are materials generally used as nonionic surfactants or slip agents, and are mainly located at the interface between the gas and the solid on the water repellent surface. As a result, it is understood that the long-chain alkyl group protrudes from the water-repellent surface, thereby pushing or rolling the water droplets formed or adhering to the water-repellent surface, thereby imparting or further improving the rolling properties.

In the present invention, the rolling angle is formed by slightly dropping 0.2cc of water on a sample to be measured on a flat surface installed on a horizontal plate to form a water drop, and the flat plate is slightly inclined at a constant speed, so that the formed water drop starts to roll. Means angle. When the sample to be measured is a permeable article such as a fabric, since the central portion may be drooped down by gravity or the like, it may be necessary to support a flat plate underneath to maintain the flat surface.

The water-repellent surface treatment composition according to the present invention can provide a rolling angle of 20 degrees or less, preferably 15 degrees or less, more preferably 10 degrees or less, and particularly preferably 5 degrees or less.

(3) acid catalyst

According to the present invention, as the acidic catalyst in step 1), an inorganic acid or an organic acid such as hydrochloric acid, acetic acid, nitric acid, sulfuric acid, phosphoric acid, or a mixed acid thereof may be included. The acidic catalyst may act as a gelling catalyst and/or a pH adjusting agent. The acidic catalyst may be an aqueous solution having a concentration of 0.001 to 1 N. If it falls within the above concentration range, the reaction time for preparing the surface treatment composition may proceed within a few days to several days.

The acidic catalyst may be used in an amount of 0.001 to 50 parts by weight, preferably 0.01 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the silicone-based crosslinking agent in step (A). In addition, in the step (B), it may be used in an amount of 0.001 to 30 parts by weight, preferably 0.01 to 10 parts by weight, and even more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the reactive silicone polymer. If it falls within the above range, not only can the speed and particle size of the sol-gel reaction be adjusted to an appropriate level, but also cloudiness or precipitation of the composition can be prevented.

(4) aqueous solvent

As the aqueous solvent that can be used in the present invention, water, an organic solvent compatible with the water, or a mixture thereof may be mentioned. The organic solvent having compatibility with water may be a water-soluble, water-miscible and/or water-soluble organic solvent, preferably an alcohol having 1 to 10 carbon atoms, more preferably methanol, ethanol, propanol, isopropanol, butanol, iso It may be selected at least one type from the group consisting of butanol, sec-butanol, ethylene glycol and propylene glycol.

The content of the aqueous solvent is selected from 10 to 300 parts by weight, preferably 50 to 200 parts by weight, more preferably 100 to 150 parts by weight, based on 100 parts by weight (solid content) of the organopolysiloxane secondary sol as a water repellent component. May be, but is not limited thereto. If it falls within the above range, the sol-gel reaction rate is appropriate, and adhesion with a substrate such as fiber can be maintained.

When a mixture of water and an organic solvent is used as the aqueous solvent, the mixing ratio thereof is 1:100 to 100:1, preferably 10:100 to 100:10, more preferably 50:100 to 100: It may be selected from the range of 50, but is not limited thereto. If it falls within the above range, it is possible to maintain adhesion with a substrate such as a fiber, and can provide excellent water repellency and transparency.

(5) Water-repellent surface and water-repellent article

According to one embodiment of the present invention, the water-repellent surface treatment composition may be applied to both an organic surface, an inorganic surface, and a metallic surface, and non-limiting examples include fiber, polymer, plastic, glass, carbon, ceramic, or metal. Can be mentioned.

According to one preferred embodiment of the present invention, the water-repellent surface treatment composition is generally a permeable article that can permeate water and air, specifically, a liquid such as water and oil, and a gas such as air and water vapor. It can provide water repellency and rollability to the permeable article. Non-limiting examples of such permeable articles may mention water repellency and rollability on the surfaces of fibers, knitted fabrics, woven fabrics and nonwovens.

Fibers and fabrics, which are the most representative examples of the permeable article, may be known natural fibers or synthetic fibers, or fabrics made of them. The water-repellent composition for fibers according to the present invention contains an organopolysiloxane sol solution having excellent adhesion or coatability to fibers, and has excellent fiber or adhesion coating properties, so it is largely limited to the material of fibers or fabrics. It can be applied universally without receiving it. Therefore, while the conventional water-repellent coating agent is excellent in coating properties for the type of fiber, that is, polyester-based fibers, the problem of remarkably deteriorating coating properties for fibers of other materials can be solved.

As a non-limiting example of the fiber, as natural fiber, cellulose fiber, protein fiber such as wool or silk fiber, mineral fiber may be used, and as synthetic fiber, polyamide fiber, polyester fiber, polyurethane fiber, acrylic fiber, olefin fiber , Polyvinyl alcohol fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, polyvinylidene dinitrile fibers, and polytetrafluoride ethylene fibers may be used. In addition, it can be applied to special fibers such as carbon fiber and aramid fiber.

In addition, the fabric may be a fabric or fabric including known natural or synthetic fibers. The term used in the present invention, the fabric or fabric is meant to include all fabrics or knitted fabrics. The fabric may be a fabric or fabric that is woven using at least one of warp and weft yarns according to the present invention.

The weaving may be made by any one method selected from the group consisting of plain weave, twill weave, weave and double weave. When these plain weave, twill weave, and weave are referred to as three-way fabrics, the specific weaving method of each three-way fabric is based on a conventional weaving method, and it may be a fabric that changes by modifying the structure or combining several fabrics based on the three-way fabric. For example, there are changeable plain weaves such as tuduk weave and basket weaves, and changeable twill weaves include new twill weaves, par twill weaves, non-twill weaves, mountain twill weaves, etc. There is this.

The double weave is a method of weaving a fabric in which either one of the warp or weft is doubled or both are doubled, and a specific method may be a conventional double weaving method.

However, it is not limited to the substrate of the fabric structure, and the density of warp yarns in weaving is not particularly limited.

In addition, the fabric may be a knitted fabric including honseom yarn as a yarn. The knitting may be performed by a weft knitting or warp knitting method, and the specific method of the weft knitting and warp knitting may be by a conventional weft knitting or warp knitting method.

(6) Surface treatment method and treated surface

The water-repellent surface treatment composition according to the present invention can be applied to a permeable article using any surface treatment, dyeing and printing method known in the art. For example, the following steps:

(1) applying the water-repellent surface treatment composition to permeable articles such as fibers or fabrics by immersion, impregnation, printing, spraying, or wetting;

(2) optionally, drying the water-repellent surface treatment composition; And

(3) heat-treating at a temperature of 150 to 170° C. for 3 to 10 minutes to form a silicon nanostructure of a three-dimensional network structure cross-linked on the surface of a fiber or fabric;

It may be performed by a method including, but is not limited to these.

According to one embodiment of the present invention, (i) natural fibers or synthetic fibers; And (ii) a crosslinked three-dimensional network structure silicon nanostructure covering the outer surface of the fiber, and (iii) the crosslinked three-dimensional network structure silicon nanostructure is a glycidoxy solution of an organopolysiloxane precursor solution. A water-repellent surface-treated fiber or fabric formed by reacting a glycidyl group of a propyl group with an amino group of an organopolysiloxane sol solution is provided, and a fabric comprising the water-repellent surface-treated fiber or fabric is provided.

The water-repellent composition for fabrics according to the present invention can be applied to fabrics by any method known in the art, for example, by any method including immersion, impregnation, spraying, printing, wetting, and the like.

Next, the fiber or fabric to which the water repellent composition has been applied is optionally dried and then fixed to form a crosslinked silicon nanostructure of a three-dimensional network structure on the fiber surface.

The fixing treatment may be performed by a method known in the art, for example, heat treatment, UV irradiation, or the like. For example, the heat treatment may be performed by hot air treatment or heat treatment for 3 to 8 minutes at a temperature of 150 to 170°C. Through this heat treatment, the organopolysiloxane can be crosslinked to form a high-density, high-durability water-repellent coating layer, through which high water repellency can be expressed. If the above temperature and time conditions are not satisfied, durability, such as part of the crosslinked product formed on the fiber surface is detached or the crosslinked product itself is peeled off the fiber surface, may significantly deteriorate.

When treating the water-repellent composition by the method described above, natural fibers or synthetic fibers; And a crosslinked three-dimensional network structure silicon nanostructure covering the outer surface of the fiber; wherein the crosslinked three-dimensional network structure silicon nanostructure includes the glycidoxypropyl group of the organopolysiloxane precursor solution. A water-repellent coated fiber containing organopolysiloxane formed by reacting a diyl group with an amino group of an organopolysiloxane sol solution can be prepared, and the crosslinked three-dimensional network structure of the silicone nanostructure has a high density, and adhesion with the fiber Remarkably excellent in durability, excellent durability, it is possible to express more improved water repellency. In addition, the N-polyoxyalkylenated fatty acid amide or O-alkylated polyglucoside is located at the gas-liquid interface of the water-repellent surface, thereby further improving the rolling property of the water-repellent surface.

According to an embodiment of the present invention, the silicon nanostructure may be bonded to the fiber surface through a covalent bond, and specifically, a hydroxyl group included in the side chain end of the organopolysiloxane, which is a silicon nanostructure, is provided on the fiber surface. It may be covalently bonded by a reaction such as dehydration and condensation with the functional group of.

In addition, the present invention provides an article surface-treated using the water-repellent surface treatment composition. The article may be a permeable article such as natural fiber, synthetic fiber, carbon fiber, knitted fabric, woven fabric and non-woven fabric, a non-permeable article such as a solar cell, a smartphone, a touch panel, a secondary battery, a display, or a car.

On the other hand, according to one advantage of the present invention, by using the cloudability improving agent as described above, it has excellent adhesion and water repellency to a substrate such as fiber, has excellent surface rollability, and is not cloudy and colorless and transparent during long-term storage. Surface treatment composition may be provided.

According to another advantage of the present invention, the water-repellent surface formed using the water-repellent surface treatment composition not only has excellent water repellency, but also excellent cloudability, so that raindrops or water droplets buried or formed on the surface can quickly flow down or roll down. As a result, it is possible to prevent or alleviate the wetting of the surface, the condensation of dew, and the resulting discomfort.

According to one variant of the present invention, by using the water-repellent surface treatment composition, the surface of the impermeable article may be treated with water repellency. For example, it may be a solar cell (back sheet), a smartphone, a touch panel, a secondary battery (corrosion prevention), a TV display (surface foreign matter removal, water blocking and fingerprint prevention), a car (rear mirror, instrument panel, etc.).

According to another advantage of the present invention, when the water-repellent surface treatment composition is used, wetting or condensation on a solid surface such as glass or metal can be significantly prevented.

The water-repellent surface treatment composition according to the present invention may be applied to a substrate as it is or diluted with a diluent. The method of application is not particularly limited, for example, impregnation, dipping, coating (e.g. dip coating, spin coating, spray coating, bar coating, roll coating, flow coating, brush coating), spraying or evaporation. I can.

The present invention will be described in more detail through the following examples, but the scope of the present invention is not limited thereto.

Example 1: Preparation of a water-repellent surface treatment composition

(A) Preparation of organopolysiloxane primary sol solution:

In a reactor equipped with a stirrer and a thermometer, 40 parts by weight of 3-glycidoxypropyltrimethoxysilane, 200 parts by weight of water and 100 parts by weight of isopropanol are mixed with respect to 100 parts by weight of tetraacetyl orthosilicate (TEOS), and While maintaining the pH at 5.0±0.2, the resulting mixture is stirred at 60° C. for 55 minutes. When the reaction mixture becomes clear, the temperature is cooled to approximately 30° C. to obtain an organopolysiloxane primary sol solution.

(B) Preparation of organopolysiloxane secondary sol solution

In the organopolysiloxane primary sol solution prepared in step (A), 0.02 parts by weight of alkyl polyglucoside (brand name: Milcoside 100; manufacturer: LG Household & Health Care) and N-polyoxyethylene cocamide (brand name: NINOL 1301; manufacturer: Stepan) 0.5 parts by weight is added and stirred vigorously to homogenize. To the resulting reaction mixture, PDMS-aminopropyl-terminated silicone oil having a viscosity of 1000 cps was dissolved in isopropyl alcohol in a weight ratio of 1: 1 and reacted at about 30° C. for 65 minutes while slowly adding 40 parts by weight of a reactive silicone polymer solution, The organopolysiloxane secondary sol solution is prepared.

To the resulting organopolysiloxane secondary sol solution, as an additive, Bluelogy ^TM Solution PE 2018 (obtained from TFJ Global), a surface treatment aid for fibers, was added in an amount of approximately 5 parts by weight based on solid content to obtain a water-repellent surface treatment composition. use.

Examples 2 and 3

Preparation was carried out in the same manner as in Example 1, but a water-repellent surface treatment composition for fabric was prepared by changing the reaction conditions and types of reactants as described in Table 1 below.

Comparative Example 1

Preparation was carried out in the same manner as in Example 1, but in step B), a water-repellent surface treatment composition for fabric was prepared by adding only a reactive silicone polymer without using a rolling property improving agent.

Comparative Example 2

Preparation was carried out in the same manner as in Example 1, but in step B), a water-repellent surface treatment composition for fabric was prepared by adding only a rolling property improving agent without using a reactive silicone polymer.

Comparative Example 3

Preparation was carried out in the same manner as in Example 1, but a water-repellent surface treatment composition for fabrics was prepared by adding a rolling property improving agent in step A) and not using a rolling property improving agent in step B) and only adding a reactive silicone polymer. .

Example 4

Proceed in the same manner as in Example 1, but by using only alkyl polyglucoside (brand name: Milcoside 100; manufacturer: LG Household & Health Care) as a rolling property improving agent, a water-repellent surface treatment composition for fabric was prepared.

Example 5

Proceeding in the same manner as in Example 1, but using only N-polyoxyethylene cocamide (brand name: NINOL 1301; manufacturer: Stepan) as a rolling property improving agent, a water-repellent surface treatment composition for fabrics was prepared.

Experimental Example 1

Polyester fibers and cotton fibers were woven in a ratio of 8:2 (basis weight 200 g/cm2), immersed in the water-repellent surface treatment composition for fabrics prepared in Example 1 and Comparative Example, and dehydrated, and slowly in a dryer. Upon drying, heat treatment at 165±5° C. for about 5 minutes will form a water-repellent coating layer. The physical properties of the water-repellent treated fabric will be measured as follows and the results will be described in Tables 1 and 2.

Water repellency test

The water repellency will be evaluated as the average water contact price by measuring the water contact angle 10 times in the water droplets formed on the surface of the water-repellent fabric treated with a contact angle meter (measured by GSA-X; manufacturer: STK Korea). The results will be shown in Tables 1 and 2.

Cloudiness test

Rolling property is made by placing the water-repellent treated fabric on a flat plate, dropping 0.2cc of water on the surface to form water droplets, tilting the flat plate at a constant speed, and measuring the cloud angle when the formed water droplets begin to roll 10 times. It will be evaluated by the angle of cloud. The results will be shown in Table 1.

Durability test of surface-treated articles

After washing the water-repellent fabric treated with the water-repellent surface treatment composition 10 times, the water contact angle and the rolling angle are measured 10 times to obtain an average value. The results will be shown in Table 1.

Experimental Example 2

The slide glass was immersed in 10 wt% NaOH aqueous solution for 5 minutes, washed with distilled water, and dried. After diluting the water-repellent surface treatment composition prepared in Examples and Comparative Examples at 0.05% by weight (solid content) in HFE-7200 (Ethoxy-nonafluorobutane; manufacturer: 3M) solvent to prepare a surface treatment composition dilution, the prepared slide glass After spin-coating at 1000 rpm, it was put in an oven and cured at 50° C. for 3 hours.

The water repellency, rolling property, and durability of the water-repellent treated slide glass were measured as in Experimental Example 1, and are shown in Tables 1 and 2.

division Ingredient type, reaction conditions and test items Example 1 Example 2 Example 3 Example 4 Example 4 Example 5 Steps (1) and (2) Silicon precursor GPTM TMPO GPTM GPTM GPTM GPTM Silicone crosslinking agent TEOS TEOS TEOS TEOS TEOS TEOS pH 4.7 4.7 4.7 4.7 4.7 4.7 Cloudiness improver - - - - - - Step (3) Type of reactive silicone polymer A type A type B type C type A type A type Viscosity of reactive silicone polymer (cps) 1000 1000 100 540 1000 1000 Cloudiness improver A type + B type A type + B type A type + B type A type + B type A type B type Configuration Organopolysiloxane sol 1st graduate+
2nd graduate 1st graduate+
2nd graduate 1st graduate+
2nd graduate 1st graduate+
2nd graduate 1st graduate+
2nd graduate 1st graduate+
2nd graduate PE
textile Contact angle 111° 109° 112° 108° 109° 110° Cloud angle 25° 26° 23° 25° 28° 27° durability 110°;25° - - - - Glass Contact angle 112° - - - 110° - Cloud angle 24° - - - 29° - durability 112°;25° - - - - - Note 1) Type of silicon precursor:
GPTM: 3-glycidoxypropyltrimethoxysilane
TMPO: [3-(trimethoxysilyl)propyl]octadecyldimethylammonium chloride
Note 2) Type of rolling property improvement agent:
Type A: alkyl polyglucoside (brand name: Milcoside 100; manufacturer: LG Household & Health Care)
Type B: N-polyoxyethylene cocamide (brand name: NINOL 1301; manufacturer: Stepan)
Note 2) Type of reactive silicone polymer
Type A: PDMS-terminated silicone oil
Type B: hydroxyl group-containing PDMS (manufacturer: KCC, brand name: OH-100)
Type C: Amino group-containing PDMS (manufacturer: Dow Coating Toray, brand name: BY 16-878)

Ingredient type, reaction conditions and test items Comparative Example 1 Comparative Example 2 Comparative Example 3 Steps (1) and (2) Silicon precursor GPTM TMPO GPTM Silicone crosslinking agent TEOS TEOS TEOS pH 4.7 4.7 4.7 Cloudiness improver - - A type + B type Step (3) Type of reactive silicone polymer A type X B type Viscosity of reactive silicone polymer (cps) 1000 X 100 Cloudiness improver - A type + B type - Configuration Organopolysiloxane sol 1st graduate+
2nd graduate 1st graduate+
2nd graduate 1st graduate+
2nd graduate PE
textile Contact angle 103° 98° 99° Cloud angle 38° 37° 34° durability - 96°;39° - Glass Contact angle - 102° - Cloud angle - 35° - durability - 100°;37° - Note) The symbols used for the types of silicon precursor, rolling property improver, and reactive silicone polymer are the same as in Table 1.

As can be seen in Tables 1 and 2, in the case of the article coated with the water-repellent surface treatment composition prepared in the embodiment of the present invention, it can be seen that the article has excellent water repellency, excellent rolling properties and long-term storage, as well as excellent durability.

The water-repellent surface treatment composition prepared in Examples 1 to 5 provides a water-repellent surface that satisfies all four factors of water repellency, rollingability, long-term storage, and durability of an article, whereas a comparative example without using a rolling property improving agent 1 is lack of long-term storage and durability, as well as rolling properties, and a rolling property improving agent is used, but when used in a manner different from the method of the present invention, the rollability and durability are secured to some extent, but long-term storage is insufficient.

In the above, preferred embodiments according to the present invention have been described with reference to the drawings and embodiments, but these are only exemplary, and various modifications and other equivalent embodiments are possible from those of ordinary skill in the art. You will be able to understand. Therefore, the scope of protection of the present invention should be determined by the appended claims.

Claims (10)

(a) as a water-repellent component, an organopolysiloxane sol prepared by adding a reactive silicone polymer solution to a mixture of a silicone precursor, a silicone crosslinking agent, and an aqueous solvent,
(b) as a cloudability improving agent, an N-polyoxyalkylenated fatty acid amide compound alone or a mixture of an N-polyoxyalkylenated fatty acid amide and an O-alkylated polyglucoside,
(c) an acidic catalyst selected from organic or inorganic acids, and
(d) aqueous solvent
Containing, a non-fluorine-based water-repellent surface treatment composition having excellent rolling properties.
The method of claim 1,
The reactive silicone polymer is selected from silicone oils containing at least one reactive functional group of carboxyl group, hydroxy group, and azo group or amino group at the end of the polymer main chain or the end of the side chain. Composition.
The method of claim 1,
The N-polyoxyalkylenated fatty acid amide is a non-fluorine-based water-repellent surface treatment composition having excellent rolling properties, characterized in that it contains a compound of the following formula (1):
[Formula 1]
RC0NH(A0) _n H or RCON[(A0) _n H] ₂
In the above formula,
R represents a substituted or unsubstituted alkyl group having 8 to 36 carbon atoms,
(A0) _n represents polyoxyethylene, polyoxypropylene or polyoxyethylene/polyoxypropylene block copolymer,
n represents the integer of 3-20.
The method of claim 1,
The O-alkylated polyglucoside is a non-fluorine-based water-repellent surface treatment composition containing a compound of the following formula (2).
[Formula 2]

In the above formula, y is 0 to 6, and R is an alkyl group having 8 to 36 carbon atoms.
The method of claim 1,
The rolling property improving agent is contained in the range of 0.001 to 20 parts by weight based on 100 parts by weight of the silicone-based crosslinking agent, a non-fluorine-based water-repellent surface treatment composition having excellent rolling properties.
The method of claim 1,
The aqueous solvent is a non-fluorine-based water-repellent surface treatment composition having excellent cloudability, characterized in that it contains water, an organic solvent compatible with water, or a mixture thereof.
A method for preparing a non-fluorine-based water-repellent surface treatment composition having excellent rolling properties according to claim 1, comprising the following steps:
(Step 1) preparing a mixture comprising a silicon precursor, a silicon-based crosslinking agent, and an aqueous solvent;
(Step 2) preparing an organopolysiloxane primary sol solution by adding an acidic catalyst to the mixture to perform a sol-gel reaction; And
(Step 3) The organopolysiloxane secondary sol, which is a reaction product of the unreacted silicone crosslinking agent and the reactive silicone polymer in the primary sol solution, by simultaneously adding a cloudability improving agent and a reactive silicone polymer solution to the organopolysiloxane primary sol solution Preparing a solution; Here, the cloudability improving agent is selected from the N-polyoxyalkylenated fatty acid amide compound alone or a mixture of N-polyoxyalkylenated fatty acid amide and O-alkyl polyglucoside .
The method of claim 7,
The step 2) is a method for producing a non-fluorine-based water-repellent surface treatment composition having excellent rolling properties, characterized in that it is carried out at 50 to 70° C. for 40 to 60 minutes.
A permeable article having excellent water repellency and rollability, selected from the group consisting of fibers, knitted fabrics, woven fabrics or nonwoven fabrics, and treated with the non-fluorine-based water repellent surface treatment composition having excellent rolling properties according to claim 1.
Selected from the group consisting of solar cells, smartphones, touch panels, secondary batteries, displays, or automobiles, and manufactured using the non-fluorine-based water-repellent surface treatment composition having excellent rolling properties according to claim 1, excellent in water repellency and rolling properties article.